Novel phosphorescent dipyrido[3,2-a:2',3'-c]phenazine (dppz) platinum(E) bis(phenylacetylide) complexes bearing electron-donating side-arms at the 2,7-positions were synthesized, and their photoluminescence properties were investigated. These complexes afforded relatively intense phosphorescence in the reddish orange region, although the 10,13-disubstituted analogous complex exhibited fluorescence in almost the same region. The TD-DFT study indicated that the strong pi-based donors at the 2,7-positions are essential to form the emissive triplet state.